CN1613962A - Heat-resistant waterproof high-brightness luminous powder with long persistence and preparation thereof - Google Patents
Heat-resistant waterproof high-brightness luminous powder with long persistence and preparation thereof Download PDFInfo
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- CN1613962A CN1613962A CN 200410035728 CN200410035728A CN1613962A CN 1613962 A CN1613962 A CN 1613962A CN 200410035728 CN200410035728 CN 200410035728 CN 200410035728 A CN200410035728 A CN 200410035728A CN 1613962 A CN1613962 A CN 1613962A
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Abstract
A waterproof and thermal resistant high luminosity long persistence fluorescent powder is produced by: using europium (Eu2+) and dysprosium (Dy3+) as activators and magnesium and strontium aluminate as matrix. It contains two steps i.e. first, preparing fluorescent powders, second, covering jargonia and triethanolamine on it. The products are of high luminosity, long persistence, liquidity, good resistance to effect of heat and water and dispersed easily. The process is facility and operated-friendly.
Description
(I) technical field
The invention relates to heat-resistant water-resistant high-brightness long-afterglow luminescent powder and a preparation method thereof.
(II) background of the invention
The traditional ZrS series long afterglow luminescent powder has poor chemical stability, low brightness and even radioactivity. The long-afterglow luminescent materials of aluminate and silicate systems, invented in the early nineties, have been applied to articles for daily use, such as weak illumination indication signs, artware and the like, due to the advantages of good chemical stability and the like, but are limited in use in many fields due to poor heat resistance or water soaking resistance. For example, materials begin to oxidize in air above 600 ℃ and lose luminescent properties. The ceramic glaze cannot be directly used in ceramic glaze materials with the temperature of more than 600 ℃, and for example, the ceramic glaze material has poor water resistance and cannot be directly used in water media, which limits the use of the ceramic glaze material in water-based paint.
The red-light-emitting phosphor is prepared by using phosphate or silicate as a matrix, and has the name of ' long-afterglow phosphorescent material ' with the application number of 93124888 and the name of ' 99805250 and the name of ' long-afterglow red-light-emitting phosphor '. The application number is 001003309 entitled "luminous efficacy long afterglow luminous body material composition and its preparation method", mainly using strontium aluminate as matrix to prepare long afterglow luminous powder. However, the above-mentioned long-afterglow luminescent powders are inferior in brightness and afterglow brightness, and do not meet the requirements for heat resistance and water resistance.
Disclosure of the invention
In order to avoid the defects of the technology, the invention provides the long-afterglow luminescent powder with high brightness, long afterglow, heat resistance and water resistance.
The invention also aims to provide a preparation method of the heat-resistant water-resistant high-brightness long-afterglow luminescent powder.
The invention is realized by the following measures:
the invention discloses a heat-resistant water-resistant high-brightness long-afterglow luminescent powder, which is prepared by taking divalent europium and trivalent dysprosium as activators and magnesium strontium aluminate as a substrate.
In order to improve the heat resistance and the water resistance, the surface of the long-afterglow luminescent powder is respectively coated with zirconia and triethanolamine from inside to outside.
The luminescent powder has a chemical expression of SrMgAl4O8:Eu2+Dy3+Wherein Eu is2+0.001 to 0.5 mol% of Dy3+The mole fraction is 0.01-2.0, and the optimal mole ratio is as follows: eu (Eu)2+0.1-0.3 mol% of Dy3+The molar fraction is 0.5-1. The luminescent powder emits yellow-green light with the peak wavelength of 520 nm.
The other chemical expression of the raw powder of the luminescent powder is Sr2MgAl10O18:Eu2+Dy3+Wherein Eu is2+0.001 to 0.5 mol% of Dy3+The molar fraction is 0.01 to 2.0. The optimal molar ratio is as follows: eu (Eu)2+0.1-0.3 mol% of Dy3+The molar fraction is 0.5-1. The above-mentioned luminescent powder emits blue-green light having a peak wavelength of 489 nm.
The chemical expression is SrMgAl4O8:Eu2+Dy3+And has the chemical formula of Sr2MgAl10O18:Eu2+Dy3+The mixed luminescent powder prepared according to the weight ratio of 4: 6 has green light with the emission peak wavelength of 500 nm.
The preparation method of the heat-resistant water-resistant high-brightness long-afterglow luminescent powder comprises the following steps,
mixing SrCO3，MgO，a-Al2O3，Eu2O3，Dy2O3Accurately weighing the materials in proportion, adding a proper amount offluxing agent, grinding, uniformly mixing, and sintering at 1200-1600 ℃ for 2-5 hours in a reducing atmosphere to obtain luminescent raw powder; the cosolvent is H3BO3And (NH)4)2HPO4A mixture of (a);
adding zirconium oxychloride (ZrOcl) into the luminescent raw powder2.8H2O) solution, ammonia water is dripped at 60 ℃, and a layer of ZrO is coated2(ii) a After being filtered with water, the luminescent powder is prepared into 40 to 60 percent serous fluid, triethanolamine with the concentration of 50 percent is added, and a layer of triethanolamine is coated after even stirring; filtering, drying at 120 deg.C, scattering and screening to obtain the invented heat-resisting water-resisting high-brightness long-afterglow luminescent powder.
The long afterglow luminescent powder prepared by the invention comprises the following raw materials: analytically pure SrCO3，MgO，a-Al2O3And a flux H3BO3、(NH4)2HPO4And fluorescent grade Eu2O3，Dy2O3。
The reaction mechanism of the present invention:
the creativity of the invention lies in that the magnesium aluminate strontium is used as the substrate to produce the long afterglow luminescent powder, which has higher afterglow luminance and longer afterglow luminescent time compared with the prior strontium aluminate, silicate and phosphate.
The surface of the luminescent powder is coated with the zirconium oxide, and the zirconium oxide has extremely high heat resistance, so that the heat resistance of the luminescent powder is improved.
The luminescent powder is coated with organic triethanolamine on the surface, and the triethanolamine has good hydrophobicity, so that the luminescent powder has good water resistance, good fluidity and easy dispersion.
The long-afterglow luminescent powder prepared by the method is not oxidized in the air at 1200 ℃, does not hydrolyze after being soaked in water for 6 months, and has the characteristics of good dispersibility and bright powder color. Meanwhile, the luminescent powder of the invention and the luminescent powder taking strontium aluminate as matrix are subjected to comparative tests according to DIN67510 test standards. The test data are as follows:
| afterglow brightness of 1min | Afterglow luminance for 10min | Afterglow luminance at 60min | |
| SrAl2O4: Eu2+Dy3+ | 2800mcd/m2 | 480mcd/m2 | 75mcd/m2 |
| According to the invention SrMgAl4O8 :Eu2+Dy3+ | 3500mcd/m2 | 550mcd/m2 | 90mcd/m2 |
In conclusion, the luminescent powder of the invention has higher afterglow luminance, longer afterglow luminescence time, better heat resistance, water resistance, good fluidity and easy dispersion.
The preparation method has the advantages of simple process, easy operation and good product quality.
(IV) detailed description of the preferred embodiments
Example 1
Weighing a-Al2O346.56g，SrCO3，33.69g，MgO9.22g，H3BO3，2.83g，(NH4)2HPO43.01g，Eu2O31.29g，Dy2O33.40g, adding corundum balls with the same weight into a porcelain ball grinding tank, fully grinding and mixing for more than 10 hours, placing the mixture into a corundum crucible, and adding N2+H2Sintering at 1300 ℃ for 3 hours under the protection of mixed gas, naturally cooling, crushing and sieving to obtain the luminescent raw powder. Putting the raw powder into a stirred zirconium oxychloride solution at 60 ℃, uniformly mixing, dropwise adding a proper amount of ammonia water, stirring for 2 hours, filtering, washing to prepare 60% slurry, adding 50% triethanolamine, uniformly stirring, filtering, drying at 120 ℃, scattering and sieving to obtain the yellowish-green heat-resistant water-resistant high-brightness long-afterglow luminescent powder.
Example 2
Weighing a-Al2O346.56g，SrCO3，33.69g，MgO9.22g，H2BO32.83g，(NH4)2HPO43.01g，EU2O31.29g，Dy2O33.40g, adding corundum balls with the same weight into a ceramic ball grinding tank, fully grinding and mixing for more than 10 hours, placing the mixture into a corundum crucible, and adding N2+H2Sintering at 1350 deg.C for 4 hr under the protection of mixed gas, naturally cooling, pulverizing, and sieving to obtain luminescent powder. Putting the raw powder into a stirred zirconium oxychloride solution with the temperature of 60 ℃, uniformly mixing, dropwise adding ammonia water, stirring for 2 hours, washing to prepare 40% slurry, adding 50% triethanolamine, uniformly stirring, drying and scattering at the temperature of 120 ℃, and sieving to obtain the blue-green light-emitting heat-resistant water-resistant high-brightness long-afterglow luminescent powder.
Example 3
40g of the heat-resistant water-resistant high-brightness long-afterglow luminescent powder emitting yellow-green light prepared according to the example 1 and 60g of the heat-resistant water-resistant high-brightness long-afterglow luminescent powder emitting blue-green light prepared according to the example 2 are weighed and mixed uniformly to prepare the heat-resistant water-resistant high-brightness long-afterglow luminescent powder emitting green light.
Claims (10)
1. A heat-resistant water-resistant high-brightness long-afterglow luminescent powder is characterized in that: the composite material is prepared by taking divalent europium and trivalent dysprosium as activators and magnesium strontium aluminateas a matrix.
2. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder as claimed in claim 1, wherein: the surface of the luminescent powder is coated with zirconium oxide and triethanolamine from inside to outside.
3. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder as claimed in claim 1 or 2, which is characterized in that: the chemical expression of the luminescent powder is SrMgAl4O8∶Eu2+Dy3+Wherein Eu is2+0.001 to 0.5 mol% of Dy3+The molar fraction is 0.01 to 2.0.
4. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder as claimed in claim 3, wherein: the Eu being2+0.1-0.3 mol% of Dy3+The molar fraction is 0.5-1.
5. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder as claimed in claim 1 or 2, which is characterized in that: the chemical expression of the raw powder is Sr2MgAl10O18∶Eu2+Dy3+Wherein Eu is2+0.001 to 0.5 mol% of Dy3+The molar fraction is 0.01 to 2.0.
6. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder according to claim 5, which is characterized in that: the Eu being2+0.1-0.3 mol% of Dy3+The molar fraction is 0.5-1.
7. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder as claimed in claim 3, wherein: the luminescent powder has yellow-green light with the emission peak wavelength of 520 nm.
8. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder as claimed in claim 5, which is characterized in that: the phosphor has a blue-green light emission peak wavelength of 489 nm.
9. The heat-resistant water-resistant high-brightness long-afterglow luminescent powder according to claim 1 or 2, characterized in that: has a chemical formula of SrMgAl4O8∶Eu2+Dy3+And has the chemical formula of Sr2MgAl10O18∶Eu2+Dy3+The mixed luminescent powder prepared according to the weight ratio of 4: 6 has green light with the emission peak wavelength of 500 nm.
10. The preparation method of the heat-resistant water-resistant high-brightness long-afterglow luminescent powder as defined in claim 2, which is characterized in that: comprises the following steps of (a) carrying out,
mixing SrCO3，MgO，a-Al2O3，Eu2O3，Dy2O3Accurately weighing the raw materials in proportion, adding a proper amount of fluxing agent, grinding, uniformly mixing, and sintering at 1200-1600 ℃ for 2-5 hours in a reducing atmosphere to obtain the finished productPolishing raw powder; the cosolvent is H3BO3And (NH)4)2HPO4A mixture of (a);
adding zirconium oxychloride solution into the luminescent raw powder, dripping ammonia water at 60 ℃, and firstly coating a layer of ZrO2(ii) a After being filtered with water, the luminescent powder is prepared into 40 to 60 percent serous fluid,triethanolamine with the concentration of 50 percent is added, and a layer of triethanolamine is coated after even stirring; filtering, drying at 120 deg.C, scattering and screening to obtain the invented heat-resisting water-resisting high-brightness long-afterglow luminescent powder.
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| CN 200410035728 CN1259389C (en) | 2004-09-09 | 2004-09-09 | Heat-resistant waterproof high-brightness luminous powder with long persistence and preparation thereof |
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| CN 200410035728 CN1259389C (en) | 2004-09-09 | 2004-09-09 | Heat-resistant waterproof high-brightness luminous powder with long persistence and preparation thereof |
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| CN1613962A true CN1613962A (en) | 2005-05-11 |
| CN1259389C CN1259389C (en) | 2006-06-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8030834B2 (en) | 2004-10-11 | 2011-10-04 | Samsung Sdi Co., Ltd. | Flat display device, plasma device panel and field emission containing phosphor coated with a heat-resistant material |
| CN102277161A (en) * | 2011-06-24 | 2011-12-14 | 合肥工业大学 | Coating modified aluminate luminescent material and coating method thereof |
| CN103881704A (en) * | 2014-03-13 | 2014-06-25 | 中国计量学院 | Orange yellow oxysulfide fluorescent powder for white light LED (Light Emitting Diode) and preparation method thereof |
| CN105315995A (en) * | 2015-12-03 | 2016-02-10 | 河北利福光电技术有限公司 | Fluxing agent and method for preparing YAG fluorescent powder |
| CN115259899A (en) * | 2022-07-25 | 2022-11-01 | 福建天蒙建设有限公司 | Method for processing multicolor long afterglow luminescent glaze |
-
2004
- 2004-09-09 CN CN 200410035728 patent/CN1259389C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8030834B2 (en) | 2004-10-11 | 2011-10-04 | Samsung Sdi Co., Ltd. | Flat display device, plasma device panel and field emission containing phosphor coated with a heat-resistant material |
| CN102277161A (en) * | 2011-06-24 | 2011-12-14 | 合肥工业大学 | Coating modified aluminate luminescent material and coating method thereof |
| CN102277161B (en) * | 2011-06-24 | 2013-11-27 | 合肥工业大学 | Coating modified aluminate luminescent material and coating method thereof |
| CN103881704A (en) * | 2014-03-13 | 2014-06-25 | 中国计量学院 | Orange yellow oxysulfide fluorescent powder for white light LED (Light Emitting Diode) and preparation method thereof |
| CN105315995A (en) * | 2015-12-03 | 2016-02-10 | 河北利福光电技术有限公司 | Fluxing agent and method for preparing YAG fluorescent powder |
| CN115259899A (en) * | 2022-07-25 | 2022-11-01 | 福建天蒙建设有限公司 | Method for processing multicolor long afterglow luminescent glaze |
| CN115259899B (en) * | 2022-07-25 | 2023-04-07 | 福建天蒙建设有限公司 | Method for processing multicolor long afterglow luminescent glaze |
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| Publication number | Publication date |
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| CN1259389C (en) | 2006-06-14 |
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